Effect of Ligand Steric Properties and Halide Identity on the Mechanism for Oxidative Addition of Haloarenes to Trialkylphosphine Pd(0) Complexes

被引:219
作者
Barrios-Landeros, Fabiola [2 ]
Carrow, Brad P. [1 ]
Hartwig, John F. [1 ]
机构
[1] Univ Illinois, Dept Chem, Urbana, IL 61801 USA
[2] Yale Univ, Dept Chem, New Haven, CT 06520 USA
关键词
PALLADIUM-CATALYZED AMINATION; ARYL HALIDES; REDUCTIVE ELIMINATION; ZEROVALENT PALLADIUM; COUPLING REACTIONS; ROOM-TEMPERATURE; AROMATIC IODIDES; HECK REACTION; PHOSPHINE; CHLORIDES;
D O I
10.1021/ja900798s
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The oxidative addition of PhX (X = I, Br, Cl) to the complexes Pd(PtBu3)(2) (1), Pd(1-AdP(t)Bu(2))(2) (2), Pd((CyPBu2)-Bu-t)(2) (3), and Pd(PCy3)(2) (4) (1-Ad = 1-adamantyl, Cy = cyclohexyl) was studied to determine the effect of steric properties on the coordination number of the species that undergoes oxidative addition and to determine whether the type of halide affects the identity of this species. The kinetic data imply that the number of phosphines coordinated to the complex that reacts in the irreversible step of the oxidative addition process for complexes 1-4 depends more on the halide than on the steric properties of the ligands. The rate-limiting step of the oxidative addition of PhI occurred with L2Pd(0) in all cases, as determined by the lack of dependence of k(obs) on [(PBu3)-Bu-t], [1-AdP(t)Bu(2)], or [(CyPBu2)-Bu-t] and the inverse dependence of the rate constant on [PCy3] when the reaction was initiated with Pd(PCy3)(3). The irreversible step of the oxidative addition of PhCl occurred with a monophosphine species in each case, as signaled by an inverse dependence of the rate-constant on the concentration of ligand. The irreversible step of the oxidative addition of PhBr occurred with a bisphosphine species, as signaled by the zeroth-order or small dependence of the rate constant on the concentration of phosphine. Thus, the additions of the less reactive chloroarenes occur through lower-coordinate intermediates than additions of the more reactive haloarenes.
引用
收藏
页码:8141 / 8154
页数:14
相关论文
共 50 条
[1]   Theoretical evidence for low-ligated palladium(0): [Pd-L] as the active species in oxidative addition reactions [J].
Ahlquist, M ;
Fristrup, P ;
Tanner, D ;
Norrby, PO .
ORGANOMETALLICS, 2006, 25 (08) :2066-2073
[2]   Oxidative addition of aryl chlorides to monoligated palladium(0): A DFT-SCRF study [J].
Ahlquist, Marten ;
Norrby, Per-Ola .
ORGANOMETALLICS, 2007, 26 (03) :550-553
[3]   Mechanistic studies of the palladium-catalyzed amination of aryl halides and the oxidative addition of aryl bromides to Pd(BINAP)2 and Pd(DPPF)2:: An unusual case of zero-order kinetic behavior and product inhibition [J].
Alcazar-Roman, LM ;
Hartwig, JF ;
Rheingold, AL ;
Liable-Sands, LM ;
Guzei, IA .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (19) :4618-4630
[4]   Mechanistic studies on oxidative addition of aryl halides and triflates to Pd(BINAP)2 and structural characterization of the product from aryl triflate addition in the presence of amine [J].
Alcazar-Roman, LM ;
Hartwig, JF .
ORGANOMETALLICS, 2002, 21 (03) :491-502
[5]   Identification of the effective palladium(0) catalytic species generated in situ from mixtures of Pd(dba)(2) and bidentate phosphine ligands. Determination of their rates and mechanism in oxidative addition [J].
Amatore, C ;
Broeker, G ;
Jutand, A ;
Khalil, F .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (22) :5176-5185
[6]   MECHANISM OF OXIDATIVE ADDITION OF PALLADIUM(0) WITH AROMATIC IODIDES IN TOLUENE, MONITORED AT ULTRAMICROELECTRODES [J].
AMATORE, C ;
PFLUGER, F .
ORGANOMETALLICS, 1990, 9 (08) :2276-2282
[7]   RATES AND MECHANISM OF THE FORMATION OF ZEROVALENT PALLADIUM COMPLEXES FROM MIXTURES OF PD(OAC)(2) AND TERTIARY PHOSPHINES AND THEIR REACTIVITY IN OXIDATIVE ADDITIONS [J].
AMATORE, C ;
CARRE, E ;
JUTAND, A ;
MBARKI, MA .
ORGANOMETALLICS, 1995, 14 (04) :1818-1826
[8]   Mechanistic and kinetic studies of palladium catalytic systems [J].
Amatore, C ;
Jutand, A .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1999, 576 (1-2) :254-278
[9]   Distinct mechanisms for the oxidative addition of chloro-, bromo-, and lodoarenes to a bisphosphine palladium(0) complex with hindered ligands [J].
Barrios-Landeros, F ;
Hartwig, JF .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (19) :6944-6945
[10]   Autocatalytic oxidative addition of PhBr to Pd(PtBu3)2 via Pd(PtBu3)2(H)(Br) [J].
Barrios-Landeros, Fabiola ;
Carrow, Brad P. ;
Hartwig, John F. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (18) :5842-+